JPH0582930B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing a silver halide color photographic material having rapid silver bleach-fixing ability.

[Prior art]

Generally, in order to obtain a color image by processing a silver halide color photographic light-sensitive material that has been imagewise exposed, a step is provided after the color development step to treat the generated metallic silver with a processing solution having bleaching ability. There is. Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, the bleaching step is usually followed by a step of fixing the silver halide with a fixing agent, but sometimes a bleach-fixing process is performed in which bleaching and fixing are performed in one step. Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions that have bleaching ability in processing silver halide color photographic light-sensitive materials. . However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate have relatively good bleaching power for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body.
It has unfavorable properties in terms of pollution prevention. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers (fixing agents) such as thiosulfates in the same processing solution, and these agents are not used in bleach-fix solutions. It is almost impossible to use oxidizing agents, which makes it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment. On the other hand, metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the requirements of speeding up and simplifying processing, and making it possible to use waste liquid for recycled paper. In recent years, treatment solutions have come to be used. However, a processing solution using a metal complex salt of an organic acid has a weak oxidizing power, and therefore has the disadvantage that the bleaching speed (oxidation speed) of the image silver (metallic silver) formed in the development step is slow. For example, iron() complex salt of ethylenediaminetetraacetate, which is considered to have the strongest bleaching power among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleaching solution and a bleach-fixing solution in some places, but silver bromide, iodine, etc. High-sensitivity silver halide color photographic materials based on silver bromide emulsions, especially color negative films and color reversal films containing silver iodide as silver halide, lack bleaching power and require long processing times. However, traces of image silver remain, resulting in poor desilvering. This tendency is particularly noticeable in a bleach-fix solution in which an oxidizing agent and thiosulfate and sulfite coexist because the redox potential is lowered. In particular, it has been found that in high-sensitivity silver iodide-containing silver halide color photographic light-sensitive materials for photographic use that contain black colloidal silver to prevent halation, the desilvering properties are markedly deteriorated. Furthermore, there is a core-shell emulsion that has recently been developed as a silver halide emulsion that is a high-sensitivity emulsion containing silver iodide, has fine grains, and effectively utilizes silver to meet the requirements for resource conservation. This is a monodisperse core-shell emulsion that is produced by using a preceding silver halide emulsion as a crystal nucleus, and then sequentially layering subsequent precipitates thereon, intentionally controlling the composition or environment of each precipitate. Among these, the core-shell type high-sensitivity emulsion containing silver iodide in the core and/or shell has extremely favorable photographic performance, but conventional bleach-fixing baths do not allow silver halide color photographic light-sensitive materials. When applied, it has been found that the bleach-fixing properties of developed silver and silver halide are extremely poor. That is, developed silver of photographic silver halide emulsions containing 0.5 mol % or more of silver iodide, especially developed silver of silver halide grains that are core-shell emulsions and containing 0.5 mol % or more of silver iodide in the core and shell. is the sensitivity,
Even if graininess, covering power, etc. are excellent, in color photographic materials in which the developed silver must be bleached, the bleaching properties are significantly poorer because the form of the developed silver is different from that of conventional materials. Especially as an emulsion in JP-A-58-
Some use tabular silver halide grains as described in, for example, No. 113930, No. 58-113934, No. 58-127921, and No. 58-108532. It is said that even if the number of photons captured by silver halide grains increases, the amount of silver used does not increase, nor does image quality deteriorate. However, even these tabular silver halide grains have the disadvantage that developed silver formed by development with a p-phenylenediamine color developing agent has poor silver bleaching properties. As a result of research, the present inventors have found that a silver halide color photographic light-sensitive material having a silver iodide-containing silver halide emulsion layer as described above and an antihalation layer made of black colloidal silver can be produced using a ferric organic acid. For rapid processing with a bleach-fix solution containing complex salts, the total thickness of all photographic layers excluding the support of the light-sensitive material and the film swelling rate T of the binder of the photographic emulsion layer are required.
It has been found that it is sufficient to reduce 1/2 to a certain value or less. That is, the present inventor has developed a high-sensitivity fine-grain silver halide color photographic light-sensitive material having black colloidal silver as an antihalation layer and at least three silver halide emulsion layers containing an emulsion containing at least 0.5 mol% silver iodide. Focusing on the phenomenon of extremely poor bleach-fixing properties, we conducted extensive research and found that the total coating silver amount and emulsion layer thickness of silver halide color photographic light-sensitive materials were below a certain value, and the binder film swelling rate was It has been found that if T1/2 is 25 seconds or less, sufficient desilvering can be achieved even with a bleach-fix solution containing an organic acid ferric complex salt. Furthermore, it has been found that when processed with a bleach-fix solution containing a combination of specific compounds according to the present invention, the time required to complete bleach-fixing of a silver iodide-containing silver halide color photographic light-sensitive material is further shortened. In particular, when the thickness of the photographic constituent layer made of a silver halide emulsion in a photographic material is reduced below a certain value according to the present invention, the bleach-fixing properties are significantly improved.
It was discovered that desilvering defects can be improved. Furthermore, surprisingly, the present inventor found that the larger the molecular weight of the organic acid in the organic acid ferric complex salt, the greater the bleaching accelerating effect due to the decrease in the swelling rate T1/2 of the binder film of the photographic constituent layer (gelatin layer). They discovered that the bleaching time was significantly reduced. On the other hand, it was also discovered that the smaller the molecular weight of the organic acid in the ferric organic acid salt, the greater the bleaching accelerating effect by reducing the thickness of the photographic constituent layer (gelatin film), and the bleach-fixing time was also significantly shortened. . That is, in general, the larger the molecular weight of the organic acid in the ferric organic acid salt, the greater the oxidizing power of silver, but the more the effect of hardening the photographic constituent layers increases, the more the diffusion and permeation of bleach-fixing components decreases, resulting in bleaching. Fixation is inhibited, and this is large compared to the thickness of the photographic constituent layers, but this inhibition does not occur if the gelatin membrane has a property of extremely rapid swelling. On the other hand, organic acid ferric complex salts with small molecular weights have a slightly weaker oxidizing power for silver, but they also have less bleach-fixing inhibition, so that the thickness of the photographic constituent layer may be reduced below a certain value according to the present invention, or gelatin may be thinned as described above. It has been found that substantially sufficient bleaching power can be obtained if the membrane swelling rate is high. Furthermore, when the thickness of the photographic constituent layer of a silver iodide-containing silver halide color photographic light-sensitive material increases, significant desilvering failure occurs at the boundary between the black colloidal silver-containing antihalation layer and the silver iodide-containing silver halide emulsion layer. It has been found that the inhibition of bleach-fixing, which is accentuated in the above, can be alleviated by thinning the photographic constituent layers to a certain value or less according to the present invention and by increasing the swelling rate of the gelatin film to a certain value or more. Therefore, according to the present invention, an innovative rapid bleach-fixing method has been discovered in which the bleach-fixing properties are not impaired even when a ferric organic acid complex salt of any molecular weight is used. However, in such rapid bleach-fixing, traces of silver inevitably remain in the photographic constituent layers.
It was discovered during the subsequent research process. In other words, the time when the emulsion film becomes transparent is generally considered to be the end of bleach-fixing, but residual silver at this time is hardly detected by spectral absorption at 1000 nm, and of course, the emulsion film is completely transparent even when visually observed. So silver cannot be confirmed. However, traces of silver are always detected with fluorescent X-rays. This is also confirmed from electron micrographs. The reason why it is usually preferable to continue the treatment for at least twice the time the emulsion film becomes transparent is considered to be to completely desilver this trace of silver. If even traces of silver remain in the photographic constituent layers, the basic gradation of the emulsion will often be subtly intensified in order to absorb all the blue, green, and red light during printing. do. Furthermore, during long-term storage of images, they undergo gradual changes (for example, silver sulfide), causing yellow stains and the like, which is a serious problem for color photosensitive materials that require stable color image storage for over a century. Therefore, there is a need for a bleach-fixing process that does not impair rapid processability and does not leave even traces of silver.

[Purpose of the invention]

First, an object of the present invention is to provide an excellent bleach-fixing method for highly sensitive fine-grain type, high-sensitivity silver iodide-containing silver halide color photographic light-sensitive materials that can achieve both resource conservation and ultra-high sensitivity. be. Second, it enables rapid processing of high-sensitivity color photographic materials,
Another object of the present invention is to provide a processing method using a bleach-fixing solution in which silver is completely removed.

[Structure of the invention]

As a result of intensive research, the present inventor has found that the present inventor has a photographic constituent layer including blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and a black colloidal silver antihalation layer, and at least one silver halide emulsion layer. but
Contains 0.5 to 25 mol% silver iodide, and the green-sensitive silver halide emulsion layer contains a magenta coupler represented by the following general formula [CI], and the thickness of all photographic constituent layers excluding the support. A silver halide color photographic light-sensitive material having a total of 8 to 25 μm, a total coated silver amount of 20 to 50 mg/dm ² , and a film swelling rate T1/2 of the binder in the photographic emulsion layer of 25 seconds or less. The object of the present invention can be achieved by processing with a bleach-fix solution containing at least one organic acid ferric complex salt and at least one of the following compounds (1) to (30) after imagewise exposure and development. was found to be achieved. General formula [CI]

[Formula] In the formula, Z represents a group of nonmetallic elements necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent.

【formula】

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【formula】

[Formula] (5) HS−CH ₂ CH ₂ −COOH

【formula】

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[ka]

【formula】

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【formula】

[ka]

[ka]

[Formula] (28) HSCH ₂ CH ₂ NHCH ₂ CH ₂ OH

【formula】 or

embedded image Preferably, the organic acid ferric complex salt is selected from (a) to (q) described in claim 9. Here, the photographic constituent layer is a layer that is on the same side as the support surface coated with at least three blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers of the present invention and participates in image formation. Refers to all hydrophilic colloid layers, and is particularly effective when there is a black colloidal silver antihalation layer.In addition to this, in addition to silver halide emulsion layers, there are also subbing layers, intermediate layers (mere intermediate layers, filter layers). , ultraviolet absorbing layer, etc.), protective layer, etc. According to a preferred embodiment of the present invention, the film thickness of the photographic constituent layer of the silver halide color photographic light-sensitive material is
22 μm or less, particularly preferably 20 μm or less,
The film swelling rate T1/2 of the binder is 20 seconds or less, particularly preferably 15 seconds or less, most preferably 10 seconds or less, and the organic acid forming the organic acid ferric complex salt is the following compound. . It has been found that the objects of the present invention can be effectively achieved by these methods. (a) Diethylenetriaminepentaacetic acid (b) Cyclohexanediaminotetraacetic acid (c) Triethylenetetraminehexaacetic acid (d) Glycoletherdiaminetetraacetic acid (e) 1,2-diaminopropanetetraacetic acid (f) 1,3-diaminopropane- 2-oltetraacetic acid (g) Ethylenediaminedi-o-hydroxyphenylacetic acid (h) Ethylenediaminetetraacetic acid (i) Nitrilotriacetic acid (j) Iminodiacetic acid (k) Methyliminodiacetic acid (l) Hydroxyethyliminodiacetic acid ( m) Ethylenediaminetetrapropionic acid (n) Dihydroxyethylglycine (o) Nitrilotripropionic acid (p) Ethylenediaminediacetic acid (q) Ethylenediaminedipropionic acid In the most effective embodiment, bleaching is performed after color development. It has been found that the above-mentioned object of the present invention can be most effectively achieved by a processing method in which fixing processing is performed as a pre-processing step of fixing processing. Hereinafter, this fixing treatment will be referred to as a pre-fixing treatment or pre-fixing, and the processing liquid used in the pre-fixing treatment will be referred to as a pre-fixing treatment liquid or pre-fixer, or a pre-fixing treatment bath or a pre-fixing bath. The present invention will be explained in more detail below. First, the magenta coupler represented by the general formula [CI] used in the present invention will be explained. General formula [CI]

[Formula] In the general formula [CI], Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group,
Sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group,
Aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group , an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 1 carbon atoms.
32, alkenyl groups, alkynyl groups with 2 to 32 carbon atoms, cycloalkyl groups, cycloalkenyl groups with 3 to 12 carbon atoms, especially 5 to 7 carbon atoms
Preferred are alkyl groups, alkenyl groups,
Alkynyl groups may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, etc. substituted through the nitrogen atom, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc. Substitution via an atom, substitution via a phosphorus atom such as phosphonyl, etc.}]. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α-
(2″-4″-di-t-amylphenoxy)butanamide]phenyl}-propyl group, 4-[α-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amyl phenyl group, 4
-tetradecanamide phenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamide] phenyl group, etc. The heterocyclic group represented by R is 5- A 7-membered group is preferable, and may be substituted or condensed. Specific examples thereof include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group. Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α
-2,4-di-t-amylphenoxybutanoyl group and other alkylcarbonyl groups, benzoyl groups, 3
Examples include arylcarbonyl groups such as -pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R include methylsulfonyl groups, alkylsulfonyl groups such as dodecylsulfonyl groups, benzenesulfonyl groups, and arylsulfonyl groups such as p-toluenesulfonyl groups. Examples of the sulfinyl group represented by R include ethylsulfinyl group, octylsulfinyl group, 3-
Alkylsulfinyl group such as phenoxybutylsulfinyl group, phenylsulfinyl group, m-
Examples include arylsulfinyl groups such as pentadecyl phenylsulfinyl groups. The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group,
Examples thereof include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups. The carbamoyl group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), for example, N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2
-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
N-{3-(2,4-di-t-amylphenoxy)
propyl}carbamoyl group, and the like. The sulfamoyl group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), for example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-
Examples include (2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, and N-phenylsulfamoyl group. Examples of the spiro compound residue represented by R include spiro[3,3]heptan-1-yl. Examples of the bridged carbonized compound residue represented by R include bicyclo[2.2.1]heptan-1-yl, tricyclo[3.3.1.3 ³ ' ⁷ ]decane-1-yl, 7,7-
Examples include dimethyl-bicyclo[2.2.1]heptane-1-yl. The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-
Ethoxyethoxy group, pentadecyloxy group, 2
-dodecyloxyethoxy group, phenethyloxyenoxy group and the like. The aryloxy group represented by R is preferably phenyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group, such as phenoxy group, p-
Examples include t-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R is 5 to 7
Preferably, the heterocycle has a substituent, for example, 3,
Examples include 4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazole-5-oxy group. The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-chloroacetyloxy group, etc. , benzoyloxy group, etc. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-phenylcarbamoyloxy group, etc. Can be mentioned. The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, anilino group, m
-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamideanilino group, and the like. As the acylamino group represented by R, an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group)
etc., which may further have a substituent, specifically an acetamide group, an α-ethylpropanamide group, an N-phenylacetamide group, a dodecanamide group, a 2,4-di-t-amylphenoxylene group, etc. Examples include cyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, and the like. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R may be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group,
Examples include N-methyl-N-decylureido group, N-phenylureido group, and Np-tolylureido group. The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoyl Examples thereof include an amino group, an N-phenylsulfamoylamino group, and the like. The alkoxycarbonylamino group represented by R may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, etc. It will be done. The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2
-t-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group and the like. The heterocyclic thio group represented by R is 5 to 7
A membered heterocyclic thio group is preferable, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups. In addition to carboxyl groups, examples of groups substituted via a carbon atom include, for example, the general formula

[Formula] (R' is the same as the above R, Z' is the same as the above Z, and R ₂ ' and R ₃ ' represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group). group,
Examples include hydroxymethyl group and triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups,
Examples include alkoxyoxalyloxy groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, and p-chlorobenzyloxy group. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenylcarbonyloxy groups such as cinnamoyloxy groups, and arylcarbonyloxy groups such as benzoyloxy groups. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxysalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. As the alkylthio group, butylthio group, 2
-cyanoethylthio group, phenethylthio group, benzylthio group, etc. The arylthio group includes phenylthio group, 4
-Methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidephenethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5-t-butylphenylthio group, etc. can be mentioned. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

Examples include those represented by [Formula]. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ′ and R ₅ ′ may be combined to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide group. group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbolamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, Examples include cyano group and halogen atom. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-ethylhexyl group.
Examples include chloroethyl group. The aryl group represented by R ₄ ' and R ₅ ' has 6 to 32 carbon atoms, and is preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent. Examples of substituents for the alkyl group represented by ₄ ' or _R5 ' include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, and 4-naphthyl group.
Examples include methylsulfonylphenyl group. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-furyl group, 2-quinolyl group, 2-pyrimidyl group,
-benzothiazolyl group, 2-biridyl group, etc. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, These alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. Examples of the carbamoyl group represented by R ₄ ' or R ₅ ' include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc. The alkyl group and aryl group may have the substituents listed for the alkyl group and aryl group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl, N-dodecylcarbamoyl group, Np-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, etc. . The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R ₄ ' or R ₅ ' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. It may also be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolyldinyl group, 2- N-1,1-dioxo-3-
(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group,
1-isoindolinyl group, 2-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-(1,
2,4-triazolyl) group, 1-(1,2,3-
triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,
3,4-tetrahydroquinolyl group, 2-oxo-
Examples include 1-pyrrolidinyl group, 2-1H-pyridone group, phthaladione group, 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl groups,
Aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group , an aryloxycarbonyl group, an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned. In addition, general formula [c] and general formula [C] described below
Substituents on the heterocycle in ~[C] (for example,
R, R ₁ to R ₈ ) is

[Formula] part (here R″, X and Z″ are R, X and Z″ in general formula [C],
It is synonymous with Z. ), it forms a so-called screw-type coupler, which is, of course, included in the present invention.
Further, the ring formed by Z, Z', Z'' and Z ₁ described below may be further fused with another ring (for example, a 5- to 7-membered cycloalkene). For example, in the general formula [C
In formula [C], R ₅ and R ₆ may be bonded to each other, and R ₇ and R ₈ may be bonded to each other to form a ring (eg, 5- to 7-membered cycloalkene, benzene). More specifically, what is represented by the general formula [C] is represented by, for example, the following general formulas [C] to [C]. General formula [C]

【formula】 General formula [C]

【formula】 General formula [C]

【formula】 General formula [C]

【formula】 General formula [C]

【formula】 General formula [C]

[Formula] In the general formulas [C] to [C], R ₁ to
R ₈ and X have the same meanings as R and X above. Also, among the general formulas [C], those represented by the following general formula [C] are preferred. General formula [C]

[Formula] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [C]. Among the magenta couplers represented by the general formulas [C] to [C], the magenta coupler represented by the general formula [C] is particularly preferred. Regarding the substituents on the heterocycle in general formulas [C] to [C], R in general formula [C] and R ₁ in general formulas [C] to [C] meet the following condition 1. It is preferable that the following conditions are satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2 Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R ₁ on the heterocycle are those represented by the following general formula [C]. General formula [C]

[Formula] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group , sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group , amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, hetero represents a ring thio group,
At least two of R ₉ , R ₁₀ and R ₁₁ are not hydrogen atoms. Also, two of the above R ₉ , R ₁₀ and R ₁₁ , for example R ₉
and R ₁₀ may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be further bonded to the ring to form a bridged hydrocarbon compound residue. You may. The group represented by R ₉ to _{R 11} may have a substituent, and specific examples of the group represented by R ₉ to R ₁₁ and the substituents that the group may have are the same as those mentioned above. Specific examples of the group represented by R in formula [C] and substituents are listed. Also, for example, a ring formed by combining R ₉ and R ₁₀ and
Specific examples of the bridged hydrocarbon compound residue formed by R ₉ to _{R 11} and its optional substituents include cycloalkyl, cycloalkenyl, and heterocycle represented by R in the above general formula [C]. Specific examples of the radical-bridged hydrocarbon compound residues and their substituents are listed. Among the general formula [C], (i) two of R ₉ to R ₁₁ are alkyl groups, and (ii) one of R ₉ to R ₁₁ , for example R ₁₁ , is a hydrogen atom. Then, when the other two R ₉ and R ₁₀ combine to form a cycloalkyl with the root carbon atom, then. Further preferred among (i) is the case where two of R ₉ to _{R 11} are alkyl groups and the other one is a hydrogen atom or an alkyl group. Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substitution represented by R in the general formula [C]. Specific examples of the group are listed below. In addition, substituents that the ring formed by Z in general formula [C] and the ring formed by Z ₁ in general formula [C] may have, and general formula [C]
] to [C], R ₂ to _{R 8} are preferably those represented by the following general formula [C]. General formula [C] -R ¹ -SO ₂ -R ² In the formula, R ¹ represents alkylene, and R ² represents alkyl, cycloalkyl or aryl. The alkylene represented by R ¹ preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms.
It does not matter whether it is straight chain or branched. Moreover, this alkylene may have a substituent. Examples of the substituent include the above-mentioned general formula [C]
When R is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of alkylene represented by R ¹ are shown below. −CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

【formula】

[Formula] −CH ₂ CH ₂ CH ₂ CH ₂ −,

【formula】

【formula】

[Formula] The alkyl group represented by R ² may be linear or branched. Specifically, methyl, ethyl, propyl, iso-
Propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, 2-hexyldecyl, and the like. The cycloalkyl group represented by R ² is 5-
A 6-membered one is preferred, such as cyclohexyl. The alkyl and cycloalkyl represented by R ² may have a substituent, examples of which include the above-mentioned substituents.
Examples of substituents for R ¹ include those exemplified. Specifically, the aryl represented by R ² is:
Examples include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as those exemplified as the substituent for R ¹ above. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula [C], those represented by the following general formula [CXI] are particularly preferred. General formula [CXI]

[C] In the formula, R and X are R and X in the general formula [C]
R ¹ and R ² have the same meaning as R ¹ and R ² in general formula [C]. Specific examples of the compounds used in the present invention are shown below, but the present invention is not limited thereto. It also includes polymer couplers having a pendant structure.

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[Exemplary compounds]

(A-1) Nickel chloride (A-2) Nickel nitrate (A-3) Nickel sulfate (A-4) Nickel acetate (A-5) Nickel bromide (A-6) Nickel iodide (A-7) Phosphorus Nickel acid (A-8) Bismuth chloride (A-9) Bismuth nitrate (A-10) Bismuth sulfate (A-11) Bismuth acetate (A-12) Zinc chloride (A-13) Zinc bromide (A-14) Zinc sulfate (A-15) Zinc nitrate (A-16) Cobalt chloride (A-17) Cobalt nitrate (A-18) Cobalt sulfate (A-19) Cobalt acetate (A-20) Cerium sulfate (A-21) Chloride Magnesium (A-22) Magnesium chloride (A-23) Magnesium acetate (A-24) Calcium chloride (A-25) Calcium nitrate (A-26) Barium chloride (A-27) Barium acetate (A-28) Barium nitrate (A-29) Strontium chloride (A-30) Strontium acetate (A-31) Strontium nitrate (A-32) Manganese chloride (A-33) Manganese sulfate (A-34) Manganese acetate (A-35) Lead acetate ( A-36) Lead nitrate (A-37) Titanium chloride (A-38) Stannous chloride (A-39) Zirconium sulfate (A-40) Zirconium nitrate (A-41) Ammonium vanadate (A-42) Metavanazine Ammonium acid (A-43) Sodium tungstate (A-44) Ammonium tungstate (A-45) Aluminum chloride (A-46) Aluminum sulfate (A-47) Aluminum nitrate (A-48) Yttrium sulfate (A-49) ) Yttrium nitrate (A-50) Yttrium chloride (A-51) Samarium chloride (A-52) Samarium bromide (A-53) Samarium sulfate (A-54) Samarium acetate (A-55) Ruthenium sulfate (A-56) ) Ruthenium chloride These metal compounds of the present invention may be used alone or in combination of two or more. The amount used is 0.0001 metal ions per liquid used.
Preferably from mol to 2 mol, particularly preferably 0.001
It ranges from 1 mole to 1 mole. The bleaching accelerator of the present invention has the general formula [] to
It is represented by [], among which R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁸ , R ⁹ , A, B, D, Z, Z', R, R',
and R and R ¹ , R ² and R ³ , R ⁴ and R ⁵ ,
The heterocyclic residue, amino group, aryl group, alkenyl group, and alkylene group formed by Q and Q' may each be substituted. Substituents include alkyl groups, aryl groups, alkenyl groups, cyclic alkyl groups, aralkyl groups, cyclic alkenyl groups, halogen atoms, nitro groups, cyano groups, alkoxy groups, aryloxy groups, carboxy groups, alkoxycarbonyl groups, and aryloxy groups. Carbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, heterocyclic residue, arylsulfonyl group, alkylsulfonyl group, alkylamino group, dialkylamino group, anilino group, N-
Alkylanilino group, N-arylanilino group,
Examples include N-acylanilino group and hydroxy group. In addition, the above R ¹ to R ⁵ , R ⁸ , R ⁹ , Z′,
The alkyl group represented by R and R' may also have a substituent, and examples of the substituent include all those listed above except for the alkyl group. The bleach-fix solution of the present invention contains an organic acid ferric complex salt (hereinafter referred to as the organic acid ferric complex salt of the present invention) as a bleaching agent. The following are representative examples of the organic acids that form the organic acid ferric complex salt of the present invention. (1) Diethylenetriaminepentaacetic acid (MW=
393.27) (2) Diethylenetriaminepentamethylenephosphonic acid (MW=573.12) (3) Cyclohexanediaminotetraacetic acid (MW=
364.35) (4) Cyclohexanediaminetetemethylenephosphonic acid (MW=508.23) (5) Triethylenetetraminehexaacetic acid (MW=
364.35) (6) Triethylenetetramine hexamethylenephosphonic acid (MW=710.72) (7) Glycol ether diamine tetraacetic acid (MWP380.35) (8) Glycol ether diamine tetramethylene phosphonic acid (MW=524.23) (9) 1. 2-diaminopropanetetraacetic acid (MW=
306.27) (10) 1,2-diaminopropane tetramethylenephosphonic acid (MW=450.15) (11) 1,3-diaminopropan-2-oltetraacetic acid (MW=322.27) (12) 1,3-diaminopropane- 2-ol tetramethylene phosphonic acid (MW=466.15) (13) Ethylenediamine diorthohydroxyphenyl acetic acid (MW=360.37) (14) Ethylenediamine diorthohydroxyphenyl methylene phosphonic acid (MW=432.31) (15) Ethylenediamine tetramethylene Phosphonic acid (MW=436.13) (16) Ethylenediaminetetraacetic acid (MW=292.25) (17) Nitrilodiacetic acid (MW=191.14) (18) Nitrilotrimethylenephosphonic acid (MW=
299.05) (19) Iminodiacetic acid (MW=133.10) (20) Iminodimethylenephosphonic acid (MW=
205.04) (21) Methyliminodiacetic acid (MW=147.13) (22) Methyliminodimethylenephosphonic acid (MW
=219.07) (23) Hydroxyethyliminodiacetic acid (MW=
177.16) (24) Hydroxyethylimino dimethylene phosphonic acid (MW=249.10) (25) Ethylenediaminetetrapropionic acid (MW=348.35) (26) Hydroxyethylglycidine (MW=
163.17) (27) Nitrilotripropionic acid (MW=233.22) (28) Ethylenediaminediacetic acid (MW=176.17) (29) Ethylenediaminedipropionic acid (MW=
277.15) The organic acid ferric complex salt of the present invention is not limited to these, but one type can be arbitrarily selected and used from these, and two or more types can also be used in combination as necessary. Among the organic acids forming the organic acid ferric salt of the present invention, the following are particularly preferred. (1) Diethylenetriaminepentaacetic acid (MW=
393.27) (3) Cyclohexanediaminotetraacetic acid (MW=
364.35) (5) Triethylenetetraminehexaacetic acid (MW=
494.45) (7) Glycol ether diamine tetraacetic acid (MWP380.35) (9) 1,2-diaminopropane tetraacetic acid (MW=
306.27) (11) 1,3-diaminopropan-2-oltetraacetic acid (MW=322.27) (13) Ethylenediaminediorthohydroxyphenylacetic acid (MW=360.37) (16) Ethylenediaminetetraacetic acid (MW=292.25) (19 ) Iminodiacetic acid (MW=133.10) (21) Methyliminodiacetic acid (MW=147.13) (23) Hydroxyethyliminodiacetic acid (MW=
177.16) (25) Ethylenediaminetetrapropionic acid (MW=348.35) (26) Hydroxyethylglycidine (MW=
163.17) (27) Nitrilotripropionic acid (MW=233.22) (28) Ethylenediaminediacetic acid (MW=176.17) (29) Ethylenediaminedipropionic acid (MW
= 277.15) The organic acid ferric complex salt of the present invention can be used as a free acid (hydrogen acid salt), an alkali metal salt such as sodium, potassium salt, or lithium salt, or ammonium salt, or a water-soluble amine salt such as triethanolamine. Preferably, the potassium, sodium and ammonium salts are used. At least one type of these ferric complex salts may be used, but two or more types can also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed. That is, it is preferably used in an amount of 0.01 mol or more per liquid used, more preferably 0.05 to 1.0 mol. In addition, in order to reduce the concentration and replenishment of the replenisher, it is desirable to use it as a replenisher after concentrating the replenisher to maximize its solubility. The bleach-fix solution of the present invention is preferably used at a pH of 2.0 to 10.0, more preferably 3.0 to 9.5, and most preferably 4.0 to 9.0. The treatment temperature is preferably 80°C or lower, more preferably 55°C or lower, and most preferably 45°C or lower to suppress evaporation. Bleach-fixing processing time is 8
It is preferably within minutes, more preferably within 6 minutes. The bleach-fix solution of the present invention can contain various additives together with the organic acid ferric complex salt of the present invention as a bleaching agent. As additives contributing to bleach-fixing properties, in particular alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide,
It is desirable to contain ammonium iodide, sodium iodide, potassium iodide, etc. Also, solubilizers such as triethanolamine, acetylacetone,
Phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamine acids, polyethylene oxides, and other substances known to be commonly added to bleaching solutions can be appropriately added. The bleach-fix solution of the present invention includes a bleach-fix solution containing a small amount of a halide such as potassium bromide, or conversely, a bleach-fix solution containing a small amount of a halide such as potassium bromide, ammonium bromide and/or ammonium iodide, or a halogen such as potassium iodide. It is also possible to use a bleach-fix solution having a composition containing a large amount of a compound, or a special bleach-fix solution containing a combination of the bleaching agent of the present invention and a large amount of a halide such as potassium bromide. The silver halide fixing agent to be included in the bleach-fixing solution of the present invention includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate and sodium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. These fixing agents can be used in an amount within the range of dissolving 5g/or more, preferably 50g/or more, more preferably 70g/or more. The bleach-fix solution of the present invention may contain various PH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, and ammonium hydroxide. Alternatively, a combination of two or more types may be contained. Furthermore, various optical brighteners, antifoaming agents, or antifungal agents can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfurous acid, isomeric bisulfite, bisulfite adducts of aldehydes and ketone compounds, other additives, and organic solvents such as methanol, dimethylformamide, and dimethylsulfoxide are appropriately contained. be able to. In addition, a special request was made in 1970.
It is desirable to add polymers or copolymers having a vinylpyrrolidone core, such as those found in No. 51803. Other desirable compounds added to the bleach-fixing solution of the present invention to promote bleach-fixing properties include tetramethylurea, trisdimethylamide phosphate, ε-caprolactam, N-methylpyrrolidone, N-methylmorpholine, and tetraethylene glycol monophenyl. Examples include ether, acetonitrile, glycol monomethyl ether, and the like. In the processing method of the present invention, it is preferable to carry out the bleach-fixing of the present invention immediately after color development, but after carrying out processing such as washing with water, rinsing, or stopping, You may do so. Most preferably, the bleaching treatment of the present invention is performed after the prefixing treatment is performed after color development as described above, and in this case, the bleaching accelerator of the present invention may be included in the prefixing treatment. In the bleach-fixing treatment of the present invention, a stable treatment may be performed without washing with water, or a washing treatment with water may be performed and then a stabilization treatment may be performed. In addition to the above steps, dura mater, neutralization,
Various auxiliary processes may be added as necessary, such as black and white development, reversal, and washing with a small amount of water. A typical example of a preferred treatment method includes the following steps. (1) Color development → bleach-fix → water washing (2) color development → bleach-fix → small amount of water washing → water washing (3) color development → bleach-fix → water washing → stable (4) color development → bleach-fix → stable (5) color development → Bleach-fixing → 1st stable → 2nd stable (6) Color development → washing with water (or stable) → bleach-fixing → washing with water (or stable) (7) color development → pre-fixing → bleach-fixing → washing with water (8) Color development → Pre-fixing → Bleach-fixing → Stable (9) Color development → Pre-fixing → Photoconductive name → First stability → Second stability (10) Color development → Stop → Bleach-fix → Washing → Stable Among these processing steps, the present invention Since the effects of (3), (4), (5), (8) and (9) are more preferably used in the present invention, the effects of (3), (4), (5), (8) and (9) are more preferably used in the present invention. The most preferred treatment steps are (4), (5), (8) and (9). It is preferable to add various inorganic metal salts to the bleach-fix solution of the present invention. It is also preferable to add these inorganic metal salts after forming metal complex salts together with various chelating agents. A chelating agent and/or a ferric complex salt thereof other than the present invention may be added to the bleach-fix solution of the present invention. However, it is preferable to use the ferric complex salt other than the present invention in an amount of 0.45 mol % or less based on the organic acid ferric complex salt of the present invention. As mentioned above, it is preferable that the pre-fixing solution contains the bleach accelerator of the present invention, and the most preferred method is to also include the bleach accelerator in the bleach-fixing solution. However, it may be contained in only one of them. When a bleach accelerator is added only to the pre-fixing solution, the bleach accelerator is brought into the bleach-fixing solution from the pre-fixing solution by the silver halide color photographic light-sensitive material and exerts its effect. The bleach-fix solution is preferably subjected to oxidation treatment in order to return the reduced form of the iron complex salt produced in the bleach-fix solution to the oxidized form, and as the oxidation treatment, for example, an air oxidation treatment step is used. Here, the air oxidation process refers to a forced oxidation process in which air bubbles are forcibly mixed into the processing solution in the bleach tank or bleach-fix tank of an automatic processor and brought into contact with it to perform oxidation treatment. Although oxidation is included, this method is usually called aeration,
In order to increase the oxidation efficiency of the air sent out from a device such as a compressor, a diffuser with fine holes such as an air distributor is used to reduce the diameter of the air as much as possible to reduce the contact area with the liquid. It is preferable that the oxidation efficiency is high and that the oxidation is carried out by contact between the treatment liquid and bubbles sent into the liquid from the bottom of the tank. This aeration is mainly carried out within the processing tank, but it may also be carried out in batches in a separate tank, or it may be carried out in an auxiliary tank for aeration attached to the side of the tank. In particular, when regenerating the bleaching solution or bleach-fixing solution, it is preferable to perform the regeneration outside the tank solution. In the present invention, there is usually no need to consider overaeration, so aeration may be performed throughout the entire processing time, strong aeration may be performed intermittently, and any method can be used. . The smaller the diameter of the air bubbles, the better the efficiency, and this is a preferable method because it prevents it from being mixed into other liquids due to splashing or the like. In the present invention, it is also preferable to perform aeration while the automatic processing machine is stopped, and to stop the aeration during processing. Alternatively, aeration may be performed separately by leading the liquid out of the processing tank. The above air ratio is disclosed in Japanese Patent Application Laid-open Nos. 49-55336 and 51-9831.
The shower method, spray method, jet atomization method, etc. described in No. 54-95234 can be used in combination, and West German patent (OLS) 2113651
The method described in this issue can also be used. The total coating amount of silver in the silver halide color photographic light-sensitive material used in the present invention is a value including the colloidal silver filter layer and the colloidal silver antihalation layer, and is 60 mg/dm ² , particularly preferably 50 mg/dm ² or less. sometimes effective. 20 in terms of photographic performance
A silver content of mg/dm ² or more is preferable and exhibits the effects of the present invention. The photographic constituent layer film thickness (gelatin film thickness) of the silver halide color photographic light-sensitive material of the present invention refers to the photographic constituent layers excluding the support, that is, the subbing layer, antihalation layer, intermediate layer, at least three emulsion layers, This is the total thickness of all hydrophilic colloid layers such as filter layers and protective layers, and is the thickness of dried photographic constituent layers. The thickness is measured with a micrometer, and in the present invention, the total thickness of the photographic constituent layers is 25 μm or less, preferably 22 μm or less, particularly 20 μm or less,
Most preferably it is 18 μm or less. From the viewpoint of photographic performance, the thickness is preferably 8 μm or more, and the effect of the present invention is exhibited. The silver halide in the silver halide emulsion layer of the present invention contains at least 0.5 mol% of silver iodide grains, which maximizes the sensitivity and photographic properties of the silver halide color photographic light-sensitive material and the bleach-fixing performance of the present invention. Therefore, silver iodide is used in terms of photographic properties and bleach-fixing properties.
0.5 mol% to 25 mol% is preferred. In the present invention, if the content exceeds 25 mol%, the photographic properties are more preferable, but the bleach-fixing properties are significantly reduced. In the present invention, more preferably 2 mol% to 20 mol%
of silver iodide. The black colloidal silver dispersion layer for preventing halation used in the present invention has sufficient resistance to visible light (especially red light) against incident light from the support surface of the silver halide color photographic light-sensitive material or incident light from the emulsion surface. It has a high optical density. It also has a sufficiently low reflectance for light incident on the emulsion surface of the silver halide color photographic light-sensitive material. The black colloidal silver dispersion layer is desirably made of sufficiently fine colloidal silver particles from the viewpoint of reflectance and bleach-fixing properties, but if the colloidal silver particles are sufficiently finely divided, the absorption will be yellow to yellowish brown and the optical density against red light will be low. It is thought that because the grains do not increase, the grains have to become coarse to some extent, and as a result, physical development is likely to occur with these silver grains as the nucleus, and the bleach-fixing properties at the boundary with the silver halide emulsion layer become worse. It will be done.
In particular, the silver halide emulsion layer is at least 0.5 mol%
in particular when the silver halide emulsion layer closest to the support contains at least 0.5 mol % of silver iodide grains.
When silver iodide grains of It is estimated that the effects of the present invention will be particularly significant. In the present invention, the effects of the present invention are particularly effectively exhibited when processing sensitive materials containing core-shell emulsions, and some of the core-shell emulsions used are described in detail in JP-A-57-154232, etc. However, preferred silver halide color photographic light-sensitive materials have a core silver halide composition containing silver iodide.
The silver halide contains 0.1 to 20 mol%, preferably 0.5 to 10 mol%, and the shell is composed of silver bromide, silver chloride, silver iodobromide, silver chlorobromide, or a mixture thereof. Particularly preferably, the shell is a silver halide emulsion comprising silver iodobromide or silver bromide. Further, in the present invention, preferable effects can be obtained by forming the core as a substantially monodisperse silver halide grain and setting the thickness of the shell to 0.01 to 0.8 μm. The silver halide color photographic light-sensitive material of the present invention is characterized by having a silver halide emulsion layer containing 0.5 to 25 moles of silver iodide, having an antihalation layer made of black colloidal silver as the bottom layer, and completely coating the material. Silver amount is 20-50
mg/dm ² , and the film thickness of the photographic constituent layer (gelatin film thickness) excluding the support is 8 μm or more and 25 μm
Below, preferably 22 μm, more preferably 20 μm,
In particular, it is 18 μm or less. In particular, silver halide grains containing silver iodide in the core and/or shell are used, and silver halide grains consisting of silver bromide, silver chloride, silver chlorobromide, silver iodobromide, or a mixture thereof are used in the above-mentioned specific method. By concealing the core with a thick shell, the ability of silver halide grains containing silver iodide to increase sensitivity is utilized, and the disadvantageous characteristics of the grains are concealed. A silver halide emulsion having silver halide grains having a shell having the above-described specific thickness can be produced by coating these shells with silver halide grains contained in a monodisperse emulsion as a core. In addition, when the shell is silver iodobromide, the ratio of silver iodide to silver bromide is preferably 20 mol % or less. To make the core a monodisperse silver halide grain,
Particles of desired size can be obtained by the double jet method while keeping pAg constant. In addition, the production of highly monodisperse silver halide emulsions was developed by JP-A-Sho.
The method described in No. 54-48521 can be applied. A preferred embodiment of the method is a method in which a potassium iodobromide-gelatin aqueous solution and an ammonium silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. Therefore, it is to manufacture. At this time, the time function of the addition rate,
By appropriately selecting PH, pAg, temperature, etc.
Highly monodisperse silver halide emulsions can be obtained. Since the particle size distribution of a monodisperse emulsion is almost a normal distribution, the standard deviation can be easily determined. From this, if we define the width of the distribution (%) by the relational expression: standard deviation/average particle size x 100 = width of the distribution (%), then the width of the distribution that can meaningfully control the absolute thickness of the coating is It is preferable that the monodispersity is 20% or less, more preferably 10% or less. Next, the thickness of the shell covering the core must be such that it does not hide the desirable qualities of the core, and on the contrary, it must be thick enough to hide the unfavorable qualities of the core. That is, the thickness is limited to a narrow range defined by such upper and lower limits. Such a shell can be formed by depositing a soluble halide solution and a soluble silver solution onto a monodisperse core by a double jet process. For example, substantially monodisperse silver halide grains with an average grain size of 1 μm containing 2 mol % silver iodide were used as the core, and 0.2 mol % silver iodobromide was used as the shell and the coating thickness was varied. According to experiments, when a shell having a thickness of 0.85 μm was prepared, for example, monodisperse silver halide grains produced by this method had a low covering power. This is treated with a physically developable processing solution containing a solvent that dissolves silver halide.
Observation with a scanning electron microscope revealed that no developed silver filaments were present. This suggests that the optical density and even the covering power are reduced. Therefore, considering the filament form of developed silver, we thinned the thickness of the silver bromide shell while changing the average grain size of the core. As a result, the thickness of the shell was 0.8 as an absolute thickness regardless of the average grain size of the core. μm or less (preferably 0.5μ
It has been found that a large number of well-developed silver filaments are produced in m) and below, a sufficient optical density is produced, and the quality of the core for high sensitivity is not impaired. On the other hand, if the thickness of the shell is too thin, parts of the core material containing silver iodide will be exposed, and the effect of coating the shell on the surface, that is, the performance such as chemical sensitization effect, rapid development and quick fixing properties, will be reduced. Lost. The thickness limit is preferably 0.01 μm. Furthermore, when confirmed by a highly monodisperse core with a distribution width of 10% or less, the preferred shell thickness is 0.01~
The thickness is 0.06 μm, and the most preferable thickness is 0.03 μm or less. The above-mentioned development silver filaments are sufficiently generated to improve the optical density, the high-sensitivity properties of the core are utilized to produce a sensitizing effect, and the rapid development and fixing properties are achieved due to the high The thickness of the shell due to the dispersive core is due to the synergistic effect between the shell described above and the silver halide composition of the core and shell, so if the thickness regulation of the shell can be satisfied, the shell can be As the constituent silver halide, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, or a mixture thereof can be used. Among these, silver bromide, silver iodobromide, or a mixture thereof is preferred from the viewpoint of compatibility with the core, performance stability, and storage stability. In the photosensitive silver halide emulsion used in the present invention, when silver halide precipitation of the core and shell is formed,
Doping may be performed with various metal salts or metal complex salts during or after grain growth. For example, metal salts or complex salts such as gold, platinum, palladium, iridium, rhodium, bismuth, cadmium, copper, and combinations thereof can be used. Further, excess halogen compounds generated during the preparation of the emulsion used in the present invention, salts and compounds such as nitrates and ammonium which are by-produced or become unnecessary may be removed. As a method for removal, a nude washing method, a dialysis method, a coagulation precipitation method, etc., which are commonly used in general emulsions, can be used as appropriate. Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, activated gelatin; water-soluble gold salt, water-soluble platinum salt, water-soluble palladium salt, water-soluble rhodium salt,
Chemical sensitizers such as noble metal sensitizers such as water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; chemical sensitizers such as polyamines, reduction sensitizers such as stannous chloride, etc. alone or in combination. I can feel it. Furthermore, this silver halide can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method for emulsions. For example, optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, trimethine dyes, or merocyanine dyes may be used alone or in combination (for example, supersensitization). can be sensitized. U.S. patents for these technologies
No. 2688545, No. 2912329, No. 3397060, No.
No. 3615635, No. 3628964, British Patent No. 1195302,
No. 1242588, No. 1293862, West German patent (OLS)
No. 2030326, No. 2121780, Special Publication No. 43-4936, No.
44-14030 etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material. The silver halide emulsion used in the present invention further comprises using a silver halide emulsion in which the core grains are monodisperse silver halide grains in order to form the silver halide grains contained therein. By coating the core grains with a shell, a monodisperse silver halide emulsion with a substantially uniform shell thickness can be obtained. It can be used as it is with its particle size distribution, or it can be prepared by blending two or more types of monodisperse emulsions with different average particle sizes at any time after grain formation to obtain a predetermined gradation. Good too. The silver halide emulsion used in the present invention contains a substantially monodisperse core with a distribution width of 20% or less in a proportion equal to or higher than that of an emulsion obtained by coating a shell with a substantially monodisperse core. It is desirable that the silver halide grains of the present invention be included in all the silver halide grains. However, silver halide grains other than those according to the invention may also be included within a range that does not impede the effects of the invention. The silver halide other than those of the present invention may be of the core-shell type or may be of a type other than the core-shell type, and may be monodisperse or polydisperse. In the silver halide emulsion used in the present invention, it is preferable that at least 65% by weight of the silver halide grains contained in the emulsion be the silver halide grains of the present invention, and almost all of them are silver halide grains of the present invention. It is desirable that The present invention provides that the silver halide emulsion contains at least
This includes cases where the emulsion contains tabular silver halide grains containing 0.5 mol % of silver iodide.
That is, in the emulsion of the present invention used in the silver halide emulsion layer of the present invention, the silver halide grains thereof are the above-mentioned silver iodide-containing core shell grains, and the silver halide grains are tabular silver halide grains containing iodide ( The silver iodide-containing tabular silver halide grains may be of the core-shell type or of other types.)
Any embodiment, such as a mixture with the above, is included in the present invention. The silver iodide-containing tabular silver halide grains will be explained below. The tabular silver halide grains preferably have a grain size of 5 times or more the grain thickness. The tabular silver halide grains are disclosed in JP-A-58-113930, JP-A-58-113934,
No. 58-127921, No. 58-108532, No. 59-99433
No. 59-119350, etc., and in the present invention, the particle diameter is preferably 5 times or more the particle thickness, from the viewpoint of effects on color staining and image quality. is preferably 5 to 100 times, particularly preferably 7 to 30 times.
Furthermore, the particle size is preferably 0.3 μm or more, and 0.5 to 6 μm.
Those are particularly preferably used. These tabular silver halide grains more preferably achieve the desired effects of the present invention when processing a sensitive material having one or more layers containing at least 50% by weight in at least one silver halide emulsion, and almost all of them When the above-mentioned tabular silver halide grains are used, particularly favorable effects can be obtained. It is particularly useful when the tabular silver halide grains are core-shell grains. In the case of the core shell particles, it is preferable that the requirements described for the core shell are also satisfied. Generally, tabular silver halide grains are tabular with two parallel surfaces, and therefore, "thickness" in the present invention is expressed as the distance between the two parallel surfaces constituting the tabular silver halide grain. Ru. In addition, "grain diameter" refers to the diameter of the projected surface of a tabular silver halide grain when observed in a direction perpendicular to the flat surface, and if it is not circular, the longest diameter is considered as the diameter of a circle. Assuming that, this diameter is used. The halogen composition of the tabular silver halide grains is preferably silver bromide and silver iodobromide;
In particular, silver iodobromide having a silver iodide content of 0.5 to 10 mol% is more preferable. Next, a method for producing tabular silver halide grains will be described. The tabular silver halide grains can be produced by appropriately combining methods known in the art. For example, in an atmosphere with a relatively high pAg value of pBr1.3 or less, seed crystals containing tabular silver halide grains of 40% or more by weight are formed, and silver and halogen solutions are simultaneously added while keeping the pBr value at the same level. It can be obtained by growing seed crystals while adding During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei. The size of the tabular silver halide grains can be adjusted by controlling temperature adjustment, selection of the type and amount of solvent, silver salt used during grain growth, acceleration of addition of halide, etc. When producing tabular silver halide grains, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. The amount of silver halide solvent used is 1× of the reaction solution.
10 ^-3 to 1.0% by weight is preferred, particularly 1 x 10 ^-2 to 1
x10 ^-1 % by weight is preferred. For example, as the amount of halogen solvent used increases, the silver halide grain size distribution can be made monodisperse and the growth rate can be increased. On the other hand, there is also a tendency for the thickness of silver halide grains to increase with the amount of silver halide solvent used. Examples of the silver halide solvent used include ammonia, thioethers, and thioureas. For thioethers, U.S. patents
No. 3271157, No. 3790387, No. 3574628, etc. can be referred to. When producing tabular silver halide grains, silver salt solutions (e.g.
AgNO ₃ aqueous solution) and halide solution (e.g.
A method of increasing the addition rate, amount, and concentration of KBr aqueous solution) is preferably used. For these methods there are e.g. British patents.
1335925, US Patent No. 36729000, US Patent No. 3650757,
No. 4242445, JP-A No. 55-142329, JP-A No. 55-
You can refer to the description in No. 158124, etc. The tabular silver halide grains can be chemically sensitized if necessary. Regarding the chemical sensitization method, the description of the sensitization method explained for the core shell can be referred to, but from the viewpoint of silver saving in particular, the tabular silver halide grains of the present invention may be gold sensitized, sulfur sensitized, or a combination thereof. is preferred. In the layer containing tabular silver halide grains,
It is preferable that the tabular silver halide grains are present in a weight ratio of 40% or more, particularly 60% or more, based on all the silver halide grains in the layer. The thickness of the layer containing tabular silver halide grains is
The thickness is preferably 0.5 μm to 5.0 μm, and more preferably 1.0 μm to 3.0 μm. Further, the coating amount (on one side) of tabular silver halide grains is preferably 0.5 g/m ² to 6 g/m ² , and 1
It is more preferable that it is g/m ^<2> -5g/m ^<2> . Other constituents of the layer containing tabular silver halide grains, such as binders, hardeners, antifoggants, silver halide stabilizers, surfactants, spectral sensitizing dyes, dyes, ultraviolet absorbers, etc. There is no limit, for example, Research Disclosure Volume 176,
Reference may be made to the description on pages 22-28 (December 1978). Next, a silver halide emulsion layer (hereinafter referred to as an upper silver halide emulsion layer) existing outside (on the surface side) of the layer containing the above-mentioned tabular silver halide grains.
We will describe the configuration of The silver halide grains used in the upper silver halide emulsion layer are preferably high-sensitivity silver halide grains used in ordinary direct X-ray films. The shape of the silver halide grains is preferably spherical, polyhedral, or a mixture of two or more thereof. In particular, it is preferable that spherical particles and/or polyhedral particles having a diameter/thickness ratio of 5 or less account for 60% or more (weight ratio) of the total. The average particle size is preferably 0.5 μm to 3 μm, and growth can be performed using a solvent such as ammonia, thioether, thiourea, etc., if necessary. The silver halide grains may be highly sensitive by gold sensitization, sensitization with other metals, reduction sensitization, sulfur sensitization, or a combination of two or more of these. preferable. As with the layer containing tabular silver halide grains, the other compositions of the upper emulsion layer are not limited, and the description in Research Disclosure Vol. 176 mentioned above can be referred to. In addition, the emulsion used in the present invention is
It is also preferable to include epitaxially bonded silver halide grains described in No. 103725, No. 59-133540, No. 59-162540, and the like. The silver halide emulsion of the present invention can contain various commonly used additives depending on the purpose.
For example, stabilizers and antifoggants such as azaindenes, triazoles, tetrazoles, imidazoliums, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, isoxazole-based, vinylsulfone-based, acryloyl-based,
Hardeners such as carbodiimide, maleimide, methanesulfonic acid ester, and triazine; Development accelerators such as benzyl alcohol and polyoxyethylene compounds; Chroman, Claman, bisphenol, and phosphite ester hardeners Image stabilizer;
Lubricants include waxes, glycerides of higher fatty acids, and higher alcohol esters of higher fatty acids. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used. In particular, it is preferable that these surfactants are eluted into a processing solution having bleaching ability. As the antistatic agent, diacetyl cellulose, styrene perfluoroalkyl sodium maleate copolymer, alkali salt of a reaction product of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. As a matting agent, polymethyl methacrylate,
Examples include polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Further, examples of the latex added to improve the physical properties of the film include copolymers of acrylic esters, vinyl esters, etc. and other monomers having ethylene groups. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers. In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used to prepare the emulsion and other hydrophilic colloid layer coating solutions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, Examples include proteins such as albumin and casein, cellulose derivatives such as hydroethyl cellulose and carboxymethyl cellulose, starch derivatives, and single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Ru. Examples of the support for the silver halide color photographic material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film,
Examples include polystyrene film, and furthermore, ordinary reflective supports (for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or with a reflective material) may also be used. It is appropriately selected depending on the intended use of the photosensitive material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. It is also possible to simultaneously apply two or more layers by the methods described in US Pat. No. 2,796,1791 and US Pat. No. 2,941,898. The silver halide emulsion of the present invention is a combination of the silver halide emulsion of the present invention, which has been color-sensitized and adjusted to red sensitivity, green sensitivity, and blue sensitivity, and cyan, magenta, and yellow coverrs in order to be applied to color light-sensitive materials. The method and material used for color photosensitive materials may be used, such as the method and material used for color photosensitive materials. The silver halide color photographic light-sensitive material to which the bleach-fix solution of the present invention can be applied is an internal development method (US Pat. No. 2,376,679,
2801171), as well as external development methods in which a color former is contained in the developer (US Pat. No. 2252718,
2592243, 2590970). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan coloring agents are those based on a naphthol or phenol structure and form indoaniline dyes through coupling, magenta coloring agents are those having a 5-pyrozolone ring with an active methylene group as a skeleton structure, and yellow coloring agents are As such, those having an acylacetanilide structure such as benzoylacetanilide and pivalyl acetanilide having an active methylene chain, with or without a substituent at the coupling position can be used. In this way, both so-called two-equivalent couplers and four-head couplers can be used as color formers. The black-and-white developer that can be used in the processing of the present invention is a commonly known black-and-white first developer used in processing silver halide color photographic light-sensitive materials, or a developer used in the processing of black-and-white photographic light-sensitive materials. It can contain various additives that are generally added to black and white developers. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned. The aromatic primary amine color developing agent used in the color developing solution used before processing with the bleach-fix solution of the present invention includes a variety of aromatic primary amine color developing agents that are widely used in various color photographic processes. . These developers are aminophenolic and p
-Includes phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than in the free state. Furthermore, it is generally preferable to use these compounds at a concentration of about 0.1 g to about 30 g per 1 part of the color developer, more preferably about 1 g per 1 part of the color developer.
It is used at a concentration of about 15 g to about 15 g. Examples of aminophenol-based development include o
-aminophenol, p-aminophenol, 5
-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3
-amino-1,4-dimethylbenzene and the like. Particularly useful aromatic primary amine color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl and phenyl groups may be substituted or unsubstituted. Among them, N,N-
Diethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, N,N
-dimethyl-p-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β- Hydroxyethylaminoaniline sulfate, 4-amino-3-
Methyl-N,N-diethylaniline sulfate, 4-
Amino-N-(methoxyethyl)-N-ethyl-3
-Methylaniline-p-toluenesulfonate and the like. Particularly useful color developing agents in the present invention have at least one water-soluble group (hydrophilic group) on the amino group.
This is a paraphenylenediamine color developing agent having the following formula. Representative examples of these color developing agents include the following compounds, but the present invention is not limited thereto.

【formula】

【formula】

【formula】

[ka]

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[ka]

[ka]

[ka]

[Chemical Formula] Color developing agents particularly useful in the present invention include -(CH ₂ )nCH ₂ OH, -(CH ₂ ) as substituents on the amino group.
_mNHSO2 ( _CH2 ) _nCH3 , -( _CH2 )mO( _CH2 )
It is a compound having each group of nCH ₃ , and specific examples include (1), (2), (3), (4), (6) and
(7) is mentioned. However, m and n are integers of 0 to 6, preferably 0 to 5. The paraphenylenediamine color developing agent is preferably mixed into the bleach fixing agent of the present invention. The alkaline color developer used before processing with the bleach-fix solution of the present invention contains, in addition to the aromatic primary amine color developer, various components that are usually added to color developers, such as Alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal zincates, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, a water softener, a thickening agent, etc. may optionally be contained. The pH of this generated developer is usually 7 or higher, most commonly about 10 to about 13. The bleach-fixing solution according to the present invention can be applied to color paper, color negative film, color positive film,
It can be applied to silver halide color photographic materials using the emulsion of the present invention, such as color reversal films for slides, color reversal films for movies, color reversal films for TVs, and reversal color papers, but especially when the total amount of coated silver is It is most suitable for processing high-sensitivity color photographic materials containing silver iodide with a silver iodide content of 50 mg/dm ² or less.

【Example】

The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, an antihalation layer, a red-sensitive silver halide layer, and a red-sensitive silver halide layer were coated from the support side with various auxiliary layers interposed. They were an emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and a monodisperse high-sensitivity silver halide emulsion layer was arranged on the outermost side of the blue-sensitive silver halide emulsion layer.
That is, samples were prepared as described below, but the film thickness was adjusted by varying the amount of gelatin so as to keep the amount of coated silver constant, thereby creating samples in which the dry film thickness was varied. The amount of silver coated was adjusted to approximately 47 mg/dm ² . However, the following are standard coating conditions, and each formulation was adjusted by changing the amount of gelatin to accommodate changes in film thickness. Layer 1: 0.9 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 700 nm, is added to gelatin 3 by reducing silver nitrate with hydroquinone as a reducing agent.
A dispersion liquid was prepared in step g, and an antihalation layer was applied. Layer 2...An intermediate layer made of gelatin. (Dry film thickness
0.8μm) Layer 3...2.0g of low-sensitivity red-sensitive silver iodobromide emulsion (AgI; 6 mol%), 2.0g of gelatin and 1.00g of silver iodobromide emulsion (AgI; 6 mol%)
g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-[δ-(2,
4-di-t-aminophenoxy)butyl]-2
- Naphthamide (hereinafter referred to as cyan coupler (C-
0.030 g of 1-hydroxy-4-
[4-(1-hydroxy-2-acetamide-
3,6-disulfo-2-naphthylazo)phenoxy]-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-1)) A low-speed red-sensitive silver halide emulsion layer containing 0.5 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved therein. Layer 4...1.3 g of highly sensitive red-sensitive silver iodobromide emulsion (Agl; 7 mol%), 1.4 g of gelatin and 0.39
g of cyan coupler (C-2) and 0.024 g of colored cyan coupler (CC-1) were dissolved.
Highly sensitive red-sensitive silver halide emulsion layer containing 0.18g of TCP. Layer 5... 0.04g of dibutyl phthalate (hereinafter referred to as DBP) and 1.2g of dibutyl phthalate (hereinafter referred to as DBP) in which 0.09g of 2,5-di-t-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)) was dissolved. Intermediate layer containing gelatin. Layer 6...1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (Agl; 18 mol%), 1.7 g of gelatin and 0.44
g of 1-(2,4,6-trichlorophenyl)-
3-[3-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter referred to as magenta coupler (comparison-1)), 0.064 g of 1-(2,4 ,6-trichlorophenyl)-4-(1-naphthylazo)-3-
(2-Chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)) containing 0.3g of TCP in low-sensitivity green light-sensitivity Silver halide emulsion layer. Layer 7...1.5g of highly sensitive green-sensitive silver iodobromide emulsion (Agl; 11 mol%), 1.9g of gelatin and
0.137g magenta coupler (comparison -1),
0.051g magenta coupler (M-2), 0.049
A highly sensitive green-sensitive silver halide emulsion layer containing 0.12 g of TCP in which g of colored magenta coupler (CM-1) was dissolved. Layer 8...0.3g yellow colloidal silver, 0.11g DBP in which 0.2g antifouling agent (HQ-1) was dissolved and
Yellow filter layer containing 2.1g of gelatin. Layer 9...1.02 g of low-speed blue-sensitive silver iodobromide emulsion (Agl; 4 mol%), 1.9 g of gelatin and 1.84
g of α-[4-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5-
0.93 g of [γ-(2,4-di-t-amylphenoxy)butanamide] acetanilide (hereinafter referred to as yellow coupler (Y-1)) dissolved
A low-speed blue-sensitive silver halide emulsion layer containing DBP. Layer 10...0.23 g of DBP in which 1.6 g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (Agl; 4 mol%), 2.0 g of gelatin and 0.46 g of yellow coupler (Y-1) were dissolved. Contains a highly sensitive blue-sensitive silver halide emulsion layer. Layer 11...Second protective layer made of gelatin. Layer 12...First protective layer containing 2.3g of gelatin. The dry film thickness of the photographic constituent layers of each finished sample is
There are four types of sample No. 35μm, 25μm, 20μm, and 18μm.
I gave it a rating of 1 to 4. Furthermore, as another sample, materials (Nos. 5 to 8) in which the magenta coupler in the green-sensitive silver halide emulsion layer was replaced with Comparison-2 having the same number of moles as Comparison-1, and exemplary magenta coupler M according to the present invention. Samples (Nos. 9 to 12) in which M-5 was substituted and samples (Nos. 13 to 16) in which M-44 was substituted were also prepared. In addition, the membrane swelling rate T1/2 of the binder
was heated in 20 seconds. Processing steps include color development for 3 minutes and 15 seconds, bleach fixing for 3 minutes,
The first stabilization was 2 minutes and the second stabilization was 30 seconds. Each treatment was performed at 37.8°C, and each treatment liquid was prepared according to the following formulation. [Color developer] Potassium carbonate 30g Sodium zincate 2.0g Hydroxylamine sulfate 2.0g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.0g Potassium bromide 1.2g Magnesium chloride 0.6g Sodium hydroxide 3.4 g N-ethyl-N-β-hydroxyethyl-3
-Methyl-4-aminoaniline sulfate 4.6g Add water to make 1 and pH with sodium hydroxide.
Adjusted to 10.1. [Bleach-fix solution] Ethylenediaminetetraacetic acid diammonium salt
7.5g diethylenetriaminepentaacetic acid ferric complex salt
0.35 mol Ammonium sulfite (50% solution) 10.0g Ammonium thiosulfate (70% solution) 200.0g Add water to make 1, and add ammonium hydroxide.
Adjusted to PH7.5. [First stable solution] 1-Hydroxyethylidene 1,1-diphosphonic acid 3.0g 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 1.0g Add water to make 1, and dilute with potassium hydroxide. PH7.1
Adjusted to. [Second stable solution] Formalin (37% solution) 7.0ml

[Formula] Add 1.0ml water to make 1. Exemplary compounds (1) are used as bleach accelerators in the bleach-fix solution.
0.7g per portion was added. The processed sample has a residual silver content in the green-sensitive emulsion layer.
It was measured and compared using two methods: spectral absorption at 1000 nm and fluorescent X-ray. The measurement of spectral absorption is
Measurement was performed using an optical densitometer using a 1000 nm interference filter. The results are shown in Table 1. Comparison magenta coupler (2)

【formula】

[Table] As shown in Table 1, among the constituent elements of the present invention,
Even if the film thickness and binder film swelling rate T1/2 are satisfied, traces of residual silver are observed as long as a conventional magenta coupler is used (Samples 2, 3, 46, 78).
However, by using the magenta coupler according to the present invention, a surprising effect was obtained in which traces of silver could be completely removed (Samples 10, 11, 12, 14, 15, and 16). It also shows that this trace amount of silver cannot be removed simply by thinning the film. Note that the magenta coupler is the exemplary coupler M-7, M-18, M-23, M-41, M-
The experiment was repeated using 59, M-100, M-104, M-116, and M-142, but no residual silver was detected by either the spectroscopic absorption method or the fluorescent X-ray method when the film thickness was 25 μm or less. Example 2 Using emulsions with the same composition as Samples 1, 5, 9, and 13 in Example 1, 100 mg/dm ² , 70 mg/dm ² , 30
mg/dm ² , and by changing the amount of hardening agent, the film swelling speed T was adjusted to two types, 10 seconds and 35 seconds, to create a total of 24 types of samples (Sample 17). ~
40). The film thickness was adjusted to 20 μm. The amount of residual silver was measured after processing in exactly the same manner as in Example 1 and setting the bleach-fixing time to 3 minutes. The results are shown in Table 2.

[Table] From Table 2, even if the magenta coupler of the present invention is used, if the amount of coated silver and the film swelling rate T1/2 are outside the conditions of the present invention, a trace amount of silver in the film in the final stage of desilvering will be lost. It turns out that it is not possible to completely eliminate the effect. Only when all the constituent requirements of the present invention are satisfied,
It is understood that the bleach-fixing speed is extremely high and that the practical bleach-fixing time can be significantly shortened by completely removing trace amounts of residual silver in the film. Example 3 Among the samples prepared in Example 1, those with a film thickness of 20 μm (Samples 3, 7, 11, and 15) were used, and the organic acid ferric complex salt in the bleach-fix solution was changed as shown in Table 3. We compared the effects when The results are shown in Table 3.

【table】

【table】

[Table] As is clear from Table 3, the effect of using the magenta coupler according to the present invention is sufficiently exhibited even when the organic acid ferric complex salt is varied. In the case of 1,2-diaminopropanetetraacetic acid ferric complex salt and ethylenediaminetetraacetic acid ferric complex salt, the effect is slightly reduced and a slight amount of silver remains. This suggests that there is some correlation between the molecular weight of the organic acid ferric complex salt and the oxidizing power (desilvering ability), but it is still difficult to draw a conclusion. However, in any case, the amount of residual silver is of no practical problem and does not impair the effects of the present invention. Example 4 A sample was prepared in which the magenta coupler in the green-sensitive emulsion layer was changed as shown in Table 4 below in Sample 10 of Example 1, and at the same time, the bleach accelerator added to the bleach-fix solution was changed. The treatment was performed and evaluated in the same manner as in Example 1. The results are shown in Table 4.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A photographic constituent layer including blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers and a black colloidal silver antihalation layer, wherein at least one silver halide emulsion layer has a 0.5 Contains ~25 mol% of silver iodide, and the green-sensitive silver halide emulsion layer contains a magenta coupler represented by the following general formula [CI], and has a thickness of all photographic constituent layers excluding the support. The total is 8 to 25 μm, and the total coated silver amount is 20 to 50 mg/d.
m ² and the film swelling rate T1/2 of the binder in the photographic emulsion layer is 25 seconds or less, after imagewise exposure and development, the silver halide color photographic material is treated with at least one organic acid ferric complex salt. Compound (1) below
A method for processing a silver halide color photographic light-sensitive material, comprising processing with a bleach-fix solution containing at least one of (30). General formula [CI] [Formula] [In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. ] [Formula] [Formula] [Formula] [Formula] (5) HS−CH ₂ CH ₂ −COOH [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] ] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] (28) HSCH ₂ CH ₂ NHCH ₂ CH ₂ OH [Formula] or [Formula] 2 Film swelling rate T1/2 of binder in photographic emulsion layer
2. The method for processing a silver halide color photographic material according to claim 1, wherein the time is 20 seconds or less. 3. A method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, which comprises at least one silver halide emulsion layer containing 2 to 25 mol % of silver iodide. . 4. The silver halide color photographic light-sensitive material according to claim 1, 2, or 3, characterized in that a pre-fixing treatment having a fixing ability is performed immediately before the bleach-fixing solution and after the development treatment. processing method. 5. The method for processing a silver halide color photographic material according to any one of claims 1 to 4, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 22 μm or less. . 6. The method for processing a silver halide color photographic material according to claim 5, wherein the thickness of the photographic constituent layer of the silver halide color photographic material is 20 μm or less. 7. The halogen according to any one of claims 1 to 6, wherein each of the silver halide emulsion layers contains silver halide grains containing 4 to 10 mol% of silver iodide. Processing method for silver chemical color photographic materials. 8. The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the silver halide emulsion is a core/shell type silver halide emulsion. 9. The method for processing a silver halide color photographic material according to any one of claims 1 to 8, wherein the bleach-fix solution contains a ferric complex salt of the following organic acid. (a) Diethylenetriaminepentaacetic acid (b) Cyclohexanediaminotetraacetic acid (c) Triethylenetetraminehexaacetic acid (d) Glycoletherdiaminetetraacetic acid (e) 1,2-diaminopropanetetraacetic acid (f) 1,3-diaminopropane- 2-oltetraacetic acid (g) Ethylenediaminedi-o-hydroxyphenylacetic acid (h) Ethylenediaminetetraacetic acid (i) Nitrilotriacetic acid (j) Iminodiacetic acid (k) Methyliminodiacetic acid (l) Hydroxyethyliminodiacetic acid ( m) Ethylenediaminetetrapropionic acid (n) Dihydroxyethylglycine (o) Nitrilotripropionic acid (p) Ethylenediaminediacetic acid (q) Ethylenediaminedipropionic acid